1. Field of the Invention
This invention relates to a sintered body target for transparent conductive film fabrication, used in a sputtering process or an ion plating process; a transparent conductive film used in a transparent electrode, an antistatic function, or a liquid crystal optical element for a display device, fabricated by using the target; and a transparent conductive base material comprising this transparent conductive film formed thereon.
2. Description of Related Art
Transparent conductive films that have low electric resistance and transparent conductive base materials in which the transparent conductive films are formed on transparent substrates are widely used in applications requiring their transparent and conductive properties, for example, in various applications to electric and electronic fields; flat panel displays such as liquid crystal displays and EL displays, transparent electrodes of touch panels, display devices, antistatic films, and liquid crystal optical elements. In general, as the transparent conductive films, tin-doped indium oxide films, that is, ITO (Indium-Tin-Oxide) crystal films are widely used. The ITO crystal films are excellent materials in which resistivity is low and the transmittance of light in the visible region is favorable. Formerly, most applications have been accommodated by controlling ITO characteristics.
However, new display devices, such as organic or inorganic EL elements and electronic papers, have recently been developed and requirements for transparent conductive films have been diversified so that common ITO crystal films can no longer meet the requirements.
For example, when the transparent conductive film is used as the transparent electrode of the organic EL element, it is desirable that the transparent conductive film is not the crystal film, but an amorphous film. In the ITO crystal film mentioned above, a projection structure due to crystal growth is present, and thus there is the problem that the local concentration of electric current is produced and uniform display becomes difficult That is, the amorphous film whose surface is extremely flat is required.
When the transparent conductive film is used as the anode of the organic EL element, it is desirable that its work function is rather great because positive holes are easily injected. However, the work functions of many transparent conductive films including the ITO film are less than 5 eV, and thus a value of 5 eV or more is favorable because light-emitting efficiency can be increased.
It is further desirable that the refractive index of the transparent conductive film is lower. By using the transparent conductive film that is lower in refractive index than the ITO film, the taking-out efficiency of light from a light-emitting layer can be improved, and there is the merit that an optical design is facilitated.
As another example, in the touch panel, there is a tendency that visibility is taken into much account. In order to prevent the visibility from deteriorating, the transparent conductive film with low refractive index becomes necessary. Since the refractive index of the ITO film is as high as 2.0-2.2 and the visibility is poor, the transparent conductive film with a refractive index of at least about 1.8 is required.
It is also important that the transparent conductive film is not the crystal film, but the amorphous film. In general, an oxide crystal film has the problem that its grain boundary is slight in structure and strength is impaired.
As the problem is posed by patent reference 1, the crystal film is particularly Affected by sliding to produce cracks and peeling, and hence is unsuitable for the touch panel requiring a pen input operation.
As an example other than those mentioned above, in the application to the electronic paper characterized by flexibility, the transparent conductive film that is hard to crack with respect to bending is essential. In general, it is known that the oxide crystal film has the grain boundary that is slight in structure, and is liable to crack, while the amorphous film in which the grain boundary does not exist is hard to crack. From this, it is proposed to apply an amorphous transparent conductive film as the transparent conductive film that is resistant to bending. In this application, since a substrate impaired by heat, such as a PET film, is used, it is necessary to deposit the amorphous transparent conductive film in the vicinity of room temperature. It is needless to say that the low refractive index is important for the amorphous transparent conductive film as in the touch panel.
In FIGS. 10, 11, and 12 of Japanese Patent Kokai No. 2002-313141, the work functions of individual transparent conductive films are shown. According to this publication, transparent conductive films having work functions in excess of 5 eV are limited to a (Ga, In)2O3 crystal film a GaInO3 crystal film, a ZnSnO3 crystal film, and a ZnO crystal film. That is, at present, no amorphous film exists which can be deposited at room temperature and has a work function of more than 5 eV.
Japanese Patent Kokai No. Hei 10-294182 proposes an organic electroluminescence element comprising an organic layer that contains an organic light-emitting layer, sandwiched between an anode and a cathode, in which the cathode includes, in order from a side coming in contact with the organic layer, an electron injection electrode layer, a transparent conductive film, and a metallic thin film with a resistivity of 1×10−5 Ω·cm or less, laminated one over another, and a transparent thin film layer is formed outside the cathode. In this case, an amorphous transparent conductive film using an oxide composed of indium (In), zinc (Zn), and oxygen (O) is applied.
Japanese Patent Kokai No. Hei 10-83719 sets forth a transparent conductive film in which a compound metallic oxide film containing In, Sn, and Zn, as the transparent conductive film having the properties of the high transmittance of visible light and low resistance, forms at least one kind of In4Sn3O12 crystal, or microcrystals or amorphism composed of In, Sn, and Zn, and as the composition of metal contains therein, an Sn content indicated by Sn×100/(In+Sn) is 40-60 at. % and a Zn content indicated by Zn×100 (In+Zn) is 10-90 at. %.
Japanese Patent Kokai No. Hei 8-264023 proposes a transparent conductive film in which, in a quasi-two-dimensional system indicated by an oxide containing magnesium (Mg) and indium (In), MgO—In2O3, as the transparent conductive film having a band gap of 3.4 eV and a refractive index of light of 2.0 that are almost the same as in a conventional transparent conductive film and possessing much higher conductivity than MgIn2O4 and In2O3, namely lower resistivity and excellent optical properties, an In Content indicated by In/(Mg+In) is 70-95 at. %.
However, in any of many amorphous transparent conductive films that have been proposed so far, represented by the above prior art, the work function is less than 5 eV and the refractive index is more than 2.0, and thus it is unreasonable that such films are suitable for the applications described above.
Japanese Patent Kokai No. Hei 7-182924 proposes a gallium-indium oxide (GaInO3) in which a heterovalent dopant like a quadrivalent atom is doped by a small amount. It is described that since the crystal film of this oxide is excellent in transparency and exhibits the refractive index of light as low as about 1.6, index matching with a glass substrate is improved and the electrical conductivity at nearly the same level as in a wide-band-gap semiconductor used at present can be attained. However, as discussed by T. Minami et al.: J. Vac. Sci. Technol. A17 (4) July/August 1999, pp. 1765-1772, this oxide has the work function in excess of 5 eV, but is the crystal film, not the amorphous film required for the recent display device. Additionally, in order to obtain the crystal film, it is necessary to perform the high-temperature deposition at a substrate temperature of 250-500° C. that is industrially disadvantageous. Hence, it is difficult at present to use the oxide as it is.
Further, Japanese Patent Kokai No. Hei 9-259640 proposes a transparent conductive film in which, in a quasi-two-dimensional system indicated by Ga2O3—In2O3 as the transparent conductive film having a composition range considerably different from GaInO3 which has been known so far and possessing much higher conductivity than GaInO3 and In2O3, namely lower resistivity and excellent optical properties, a Ga content indicated by Ga/(Ga+In) is 15-49 at. %. In particular, it is described that the transparent conductive film has the feature that the refractive index of light can be changed from about 1.8 to 2.1 by altering the composition. In the embodiments, however, the refractive index and the work function are not in any way suggested. More details are reported, by the inventors of Kokai No. Hei 9-259640, in T. Minami et al.: J. Vac. Sci. Technol. A17 (4), July/August 1999, pp. 1765-1772 and T. Minami et al.: J. Vac. Sci. Technol. A14 (3), May/June 1996, pp. 1689-1693.
As mentioned above, in T. Minami et al.: J. Vac. Sci. Technol. A17 (4), July/August 1999, pp. 1765-1772, the work function of the (Ga, In)2O3 crystal film deposited at a substrate temperature of 350° C. is merely shown, and the work function of the amorphous film is not suggested. In FIG. 6 of Kokai No. Hei 10-294182, the refractive indices of transparent conductive films composed of Ga, In, and O, particularly deposited at room temperatures are shown. According to this aspect, it is described that the refractive index of the In2O3 film is about 2.1, the transparent conductive film in which the Ga content indicated by Ga/(Ga+In) is 5-80 at. % has a refractive index of 1.9-2.3, the refractive index of the Ga2O3 film is about 1.8, and in particular, the transparent conductive film in which the Ga content indicated by Ga/(Ga+In) is 50 at. % has a refractive index of about 2.0.
As seen from the above description, the fact is that the transparent conductive film in which the deposition in the vicinity of the room temperature is possible, amorphism is provided, the work function is above 5 eV, and the refractive index is low is not yet obtained. In the applications to the organic EL element, the touch panel, and the electronic paper, therefore, no transparent conductive film has yet completely met, in good balance, demands for a transparent conductive film that is high in work function and low in refractive index, for an amorphous transparent conductive film that is hard to crack with respect to sliding and bending, and for an amorphous transparent conductive film whose surface is extremely flat, and the need for film deposition in the vicinity of the room temperature. New transparent conductive films meeting these requirements are needed. Moreover, sintered body targets for transparent conductive film fabrication for providing the transparent conductive films by using the sputtering process or the ion plating process are also needed.